Reaction of PtRu5(CO)15(PBut 3)(C), 3, with hydrogen at 97°C yielded the new dihydride-containing cluster compound PtRu5(CO)14(PBu t3)(μ-H)2(μ6-C), 5. Compound 5 was characterized crystallographically and was shown to contain an octahedral cluster consisting of one platinum and five ruthenium atoms with a carbido ligand in the center. Two hydrido ligands bridge two oppositely positioned PtRu bonds. Compound 5 reacts with Pt(PBut3)2 to yield Pt2Ru5-(CO)14(PBut 3)2(μ-H)2(μ6-C), 6, a Pt(PBu t3) adduct of 5, by adding a Pt(PBut 3) group as a bridge across one of the Ru-Ru bonds in the square base of the Ru5 portion of the cluster. Compound 6 is dynamically active on the NMR time scale by a mechanism that appears to involve a shifting of the Pt(PBut3) group from one Ru-Ru bond to another. Two new complexes, PtRu5(CO)13(PBut3)(μ- H)3(GePh3)(μ5-C), 7, and PtRu 5(CO)13(PBut3)(μ-H) 2(μ-GePh2)-(μ6-C), 8, were obtained from the reaction of 5 with HGePh3. The cluster of 7 has an open structure in which the Pt(PBut3) group bridges an edge of the square base of the square pyramidal Ru5 cluster. Compound 7 also has three bridging hydrido ligands and one terminal GePh3 ligand. When heated to 97°C, 7 is slowly converted to 8 by cleavage of a phenyl group from the GePh3 ligand and elimination of benzene by its combination with one of the hydrido ligands. The PtRu5 metal cluster of 8 has a closed octahedral shape with a GePh2 ligand bridging one of the Ru-Ru bonds. Two tin-containing compounds, PtRu5(CO)13(PBu t3)(μ-H)3(SnPh3) (μ5-C), 9, and PtRu5(CO)13-(PBu t3)(μ-H)2(μ-SnPh2) (μ6-C), 10, which are analogous to 7 and 8 were obtained from the reaction of 5 with HSnPh3.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry